Fibre-reactive anthraquinone dyes, process for their preparation, and their use

ABSTRACT

Anthraquinone dyes of the formula ##STR1## in which R 1 , R 2 , R 3 , R 4  and R 5  independently of one another are hydrogen or are substituted or unsubstituted C 1  -C 12  alkyl, 
     X 1  and X 2  independently of one another are chlorine or fluorine, 
     B 1  is a C 2  -C 12  alkylene radical which is unsubstituted or substituted by hydroxyl, sulfo or sulfato and is uninterrupted or is interrupted by oxygen; or is a cyclohexylene radical, 
     C 1  -C 4  alkylene-cyclohexylene radical, cyclohexylene-C 1  -C 4  alkylene radical, 
     C 1  -C 4  alkylene-cyclohexylene-C 1  -C 4  alkylene radical or cyclohexylene-methylene-cyclohexylene radical which is unsubstituted or is substituted in the cyclohexylene ring by C 1  -C 4  alkyl; or is a C 1  -C 4  alkylene-phenylene radical, 
     phenylene-C 1  -C 4  alkylene radical or C 1  -C 4  alkylene-phenylene-C 1  -C 4  alkylene radical which is unsubstituted or is substituted in the phenylene ring by C 1  -C 4  alkyl, C 1  -C 4  alkoxy, 
     C 2  -C 4  alkanoylamino, sulfo, halogen or carboxyl, 
     B 2  is an aromatic bridge member, 
     Y is hydrogen, substituted or unsubstituted C 1  -C 12  alkyl, or a radical of the benzene or naphthalene series, and 
     m is the number 0 or 1, 
     with the proviso that, if m is the number 0, the radical Y contains a fibre-reactive group with the formula ##STR2## in which Hal is halogen and R&#39; is hydrogen or C 1  -C 4  alkyl, are particularly suitable for the dyeing or printing of cellulosic fibre materials or natural or synthetic polyamide fibre materials, with a high dyeing yield, and give dyeings and prints having good fastness properties.

This is a continuation of application Ser. No. 08/541,008, filed Oct.11, 1995 now U.S. Pat. No. 5,601,622.

The present invention relates to novel fibre-reactive anthraquinonedyes, to a process for their preparation and to their use for the dyeingor printing of fibre materials.

The practice of dyeing with reactive dyes has led in recent times toincreased requirements regarding the quality of the dyeings and theeconomy of the dyeing process. As a result there continues to be a needfor novel reactive dyes which have improved properties, in particularwith respect to their application.

For dyeing nowadays, reactive dyes are required which combine sufficientsubstantivity with ready ease of washoff of the unfixed portions. Theyshould in addition show a good dyeing yield and be of high reactivity,the intention being in particular to give dyeings having high degrees offixation. These requirements are not met by all of the properties of theknown dyes.

The object of the present invention is therefore to find novel, improvedreactive dyes for the dyeing and printing of fibre materials, whichpossess the qualities characterized above to a high degree. The noveldyes should in particular be distinguished by high fixation yields andhigh stabilities of the fibre-dye bonds, and, in addition, the portionsnot fixed to the fibre should be able to be washed off readily. The dyesshould, moreover, give dyeings having good all-round fastnessproperties, for example light fastness and wet fastness properties.

It has been found that the said object can be largely achieved with thenovel reactive dyes defined below.

The invention therefore provides anthraquinone dyes of the formula##STR3## in which R₁, R₂, R₃, R₄ and R₅ independently of one another arehydrogen or are substituted or unsubstituted C₁ -C₁₂ alkyl,

X₁ and X₂ independently of one another are chlorine or fluorine,

B₁ is a C₂ -C₁₂ alkylene radical which is unsubstituted or substitutedby hydroxyl, sulfo or sulfato and is uninterrupted or is interrupted byoxygen; or is a cyclohexylene radical,

C₁ -C₄ alkylene-cyclohexylene radical, cyclohexylene-C₁ -C₄ alkyleneradical,

C₁ -C₄ alkylene-cyclohexylene-C₁ -C₄ alkylene radical orcyclohexylene-methylene-cyclohexylene radical which is unsubstituted oris substituted in the cyclohexylene ring by C₁ -C₄ alkyl; or is a C₁ -C₄alkylene-phenylene radical,

phenylene-C₁ -C₄ alkylene radical or C₁ -C₄ alkylene-phenylene-C₁ -C₄alkylene radical which is unsubstituted or is substituted in thephenylene ring by C₁ -C₄ alkyl, C₁ -C₄ alkoxy,

C₂ -C₄ alkanoylamino, sulfo, halogen or carboxyl,

B₂ is an aromatic bridge member,

Y is hydrogen, substituted or unsubstituted C₁ -C₁₂ alkyl, or a radicalof the benzene or naphthalene series, and

m is the number 0 or 1,

with the proviso that, if m is the number 0, the radical Y contains afibre-reactive group with the formula ##STR4## in which Hal is halogenand R' is hydrogen or C₁ -C₄ alkyl.

Suitable C₁ -C₁₂ alkyl radicals for R₁, R₂, R₃, R₄, R₅ and Y arepreferably C₁ -C₁₀ alkyl radicals, especially C₁ -C₈ alkyl radicals. Thealkyl radicals mentioned can, with the exception of methyl, beinterrupted by, for example, oxygen, preferably by 1, 2 or 3 members--O--, in particular by 1 or 2 members --O--. The alkyl radicalsmentioned may in addition be unsubstituted or substituted by, forexample, hydroxyl, sulfo or sulfato, preferably by hydroxyl or sulfo andin particular by hydroxyl. The radical Y as alkyl can additionally besubstituted by the radical of an anthraquinone dye, such as, forexample, by a radical of 1,4-diaminoanthraquinone-2-sulfonic acid, whichradical is attached via the amino group in position 4.

Suitable C₂ -C₁₂ alkylene radicals for B₁ are preferably C₂ -C₁₀alkylene radicals, especially C₂ -C₈ alkylene radicals. C₂ -C₆ alkyleneradicals are of particular interest. The alkylene radicals mentioned canbe interrupted by, for example, oxygen, preferably by 1, 2 or 3 members--O--, in particular by 1 or 2 members --O--. The alkylene radicalsmentioned can in addition be unsubstituted or substituted by hydroxyl,sulfo or sulfato, preferably by hydroxyl or sulfo and in particular byhydroxyl. The alkylene radicals mentioned are preferably unsubstituted.Examples of such alkylene radicals are --(CH₂)₆ --, --(CH₂)₂ --O--(CH₂)₂--O--(CH₂)₂ --, --(CH₂)₃ --O--(CH₂)₄ --O--(CH₂)₃ --, --CH₂ --CH₂ --CH(C₂H₅)--, --(CH₂)₃ --CH(CH₃)--CH₂ -- and in particular --(CH₂)₃ -- and--CH₂ --C(CH₃)₂ --CH₂ --.

Suitable substituents of the cyclohexylene radicals mentioned for B₁ arein particular methyl or ethyl, preferably methyl. If, in such bridgingmembers B₁, the cyclohexylene radical is connected to a C₁ -C₄ alkyleneradical, then this C₁ -C₄ alkylene radical is preferably a methyleneradical.

The C₁ -C₄ alkylene-phenylene radicals, phenylene-C₁ -C₄ alkyleneradicals and C₁ -C₄ alkylene-phenylene-C₁ -C₄ alkylene radicalsmentioned for B₁ can be unsubstituted or substituted in the phenylenerings by, for example, C₁ -C₄ alkyl such as methyl, ethyl, propyl,isopropyl, butyl, sec-butyl, tert-butyl or isobutyl, especially methyl,by C₁ -C₄ alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy orisobutoxy, especially methoxy, by C₂ -C₄ alkanoylamino, for exampleacetylamino or propionylamino, by halogen, for example fluorine,chlorine or bromine, especially chlorine, or by sulfo or carboxyl; theyare preferably unsubstituted or substituted by C₁ -C₄ alkyl, C₁ -C₄alkoxy, halogen or sulfo. The corresponding unsubstituted radicals areof particular interest. The C₁ -C₄ alkylene radicals present in suchbridging members B₁ are preferably methylene radicals. Of particularimportance in this context are C₁ -C₄ alkylene-phenylene-C₁ -C₄ alkyleneradicals, especially methylene-phenylene-methylene radicals.

A suitable aromatic bridging member B₂ is, for example, phenylene ornaphthalene, which can be unsubstituted or substituted by, for example,C₁ -C₄ alkyl such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,tert-butyl or isobutyl, especially methyl, by C₁ -C₄ alkoxy such asmethoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, especiallymethoxy, by C₂ -C₄ alkanoylamino, for example acetylamino orpropionylamino, by halogen, for example fluorine, chlorine or bromine,especially chlorine, or by sulfo or carboxyl. The phenylene andnaphthalene radicals are preferably unsubstituted or substituted by C₁-C₄ alkyl, C₁ -C₄ alkoxy, halogen or sulfo. Of particular interest inthis context are the phenylene radicals, especially sulfo-substitutedphenylene radicals.

The phenyl and naphthyl radicals mentioned for Y can be unsubstituted orsubstituted, for example, as indicated above for B₂. The phenyl andnaphthyl radicals mentioned for Y can in addition be substituted by afibre-reactive group.

Examples of such fibre-reactive groups are those of the formulae##STR5## in which W is a group of the formula --SO₂ --NR₆ --, --CONR₆ --or --NR₆ CO--,

R₆ is hydrogen or is C₁ -C₄ alkyl which is unsubstituted or issubstituted by hydroxyl, sulfo, sulfato, carboxyl or cyano,

R is hydrogen, hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen, C₁-C₄ alkoxycarbonyl, C₁ -C₄ alkanoyloxy or carbamoyl,

R' is hydrogen or C₁ -C₄ alkyl,

Z is a group of the formula --CH═CH₂ or --CH₂ --CH₂ --U₁ and U₁ is aleaving group,

Hal is halogen,

E is the radical --O-- or --NR₇ -- and R₇ is hydrogen or C₁ -C₄ alkyl,and

alk and alk' are independently of one another C₁ -C₆ alkylene.

Examples of suitable leaving groups U₁ are --Cl, --Br, --F, --OSO₃ H,--SSO₃ H, --OCO--CH₃, --OPO₃ H₂, --OCO--CCl₃, --OCO--CHCl₂, --OCO--CH₂Cl, --OSO₂ --C₁ -C₄ alkyl, --OSO₂ --N(C₁ -C₄ alkyl)₂ or --OCO--C₆ H₅.

U₁ is preferably a group of the formula --Cl, --OSO₃ H, --SSO₃ H,--OCO--CH₃, --OCO--C₆ H₅ or --OPO₃ H₂, especially --Cl or --OSO₃ H,preferably --OSO₃ H.

alk and alk' are independently of one another, for example, a methylene,ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexyleneradical or branched isomers thereof.

alk and alk' are preferably a C₁ -C₄ alkylene radical and, withparticular preference, are an ethylene radical.

R is preferably hydrogen.

R' is preferably hydrogen.

R₆ is preferably hydrogen or C₁ -C₄ alkyl such as methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl or tert-butyl. R₆ is withparticular preference hydrogen.

E is preferably --NH-- or --O-- and with particular preference is --O--.

W is preferably a group of the formula --CONH-- or --NHCO--, especiallya group of the formula --CONH--.

Hal in the radical of the formulae (2a) and (2b) is preferably chlorineor, in particular, bromine.

Preferred reactive radicals of the formula (2a) to (2g) are those inwhich W is a group of the formula --CONH-- or --NHCO--, in particular agroup of the formula --CONH--, R is hydrogen, E is the radical --O-- or--NH--, Hal is chlorine or bromine and U₁ is a group of the formula--Cl, --OSO₃ H, --SSO₃ H, --OCO--CH₃, --OCO--C₆ H₅ or --OPO₃ H₂, inparticular a group of the formula --Cl or --OSO₃ H. R' is preferablyhydrogen.

Particularly preferred reactive radicals are those of the formulae (2a)to (2d) in which the abovementioned definitions and preferences applyfor Hal, Z, W, R and R'.

R₁, R₂, R₃ and R₄ are preferably hydrogen or C₁ -C₄ alkyl, especiallyhydrogen.

R₅ is preferably hydrogen or C₁ -C₈ alkyl which is unsubstituted or issubstituted by hydroxyl, sulfo or sulfato and, with the exception ofmethyl, is uninterrupted or is interrupted by oxygen, and is preferablyhydrogen or unsubstituted or hydroxyl-substituted C₁ -C₄ alkyl, andespecially hydrogen.

R₁, R₂, R₃ and R₄ are with particular preference hydrogen or C₁ -C₄alkyl, especially hydrogen, and R₅ is hydrogen or is C₁ -C₈ alkyl whichis unsubstituted or is substituted by hydroxyl, sulfo or sulfato and,with the exception of methyl, is uninterrupted or is interrupted byoxygen, and is in particular hydrogen or unsubstituted orhydroxyl-substituted C₁ -C₄ alkyl, and is preferably hydrogen.

B₁ is preferably C₂ -C₁₂ alkylene which is uninterrupted or isinterrupted by oxygen; or is a methylene-cyclohexylene radical,cyclohexylene-methylene radical or cyclohexylene-methylene-cyclohexyleneradical which is unsubstituted or is substituted in the cyclohexylenering by C₁ -C₄ alkyl; or is a methylene-phenylene-methylene radicalwhich is unsubstituted or is substituted in the phenylene ring by C₁ -C₄alkyl, C₁ -C₄ alkoxy, halogen or sulfo.

With particular preference, B₁ is C₂ -C₁₂ alkylene which isuninterrupted or is interrupted by oxygen; or is amethylene-cylohexylene radical or cyclohexylene-methylene radical whichis unsubstituted or is substituted in the cyclohexylene ring by C₁ -C₄alkyl; or is a methylene-phenylene-methylene radical.

As the bridge member B₁, the corresponding alkylene radicals are ofparticular interest. With very particular preference, B₁ is C₂ -C₆alkylene, especially a radical of the formula --(CH₂)₃ -- or,preferably, a radical of the formula --CH₂ --C(CH₃)₂ --CH₂ --.

B₂ is preferably unsubstituted or C₁ -C₄ alkyl-, C₁ -C₄ alkoxy-, C₂ -C₄alkanoylamino-, halogen-, carboxyl- or sulfo-substituted naphthalene or,preferably, phenylene.

With particular preference, B₂ is phenylene which is unsubstituted or issubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen or sulfo, preferablysulfo-substituted phenylene.

Preferred anthraquinone dyes of the formula (1) in which m is the number1 are those in which Y is hydrogen or is C₁ -C₁₂ alkyl which isunsubstituted or substituted by hydroxyl, sulfo or sulfato and, with theexception of methyl, is uninterrupted or interrupted by oxygen; or

Y is phenyl or naphthyl, where the phenyl and naphthyl radicals can besubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino,halogen, carboxyl or sulfo or by one of the fibre-reactive groups of theformulae (2a) to (2g), in particular of the formulae (2a) to (2d); or

Y is an anthraquinone radical of the formula ##STR6## in which case, forB₁ ', the definitions and preferences indicated above for B₁ apply.

Y here is preferably hydrogen or C₁ -C₈ alkyl which is unsubstituted orsubstituted by hydroxyl, sulfo or sulfato and, with the exception ofmethyl, is uninterrupted or is interrupted by oxygen; or

is an anthraquinone radical of the formula (3); or

is sulfo-substituted naphthyl; or

is phenyl which can be substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy,halogen or sulfo or by a fibre-reactive radical of the formula (2a),(2b), (2c) or (2d), where W is a group of the formula --CO--NH--, R ishydrogen, R' is preferably hydrogen and U₁ is sulfato or chlorine.

Of particular interest for Y are the corresponding phenyl radicals.

Particularly preferred anthraquinone dyes of the formula (1) in which mis the number 1 are those in which

R₁, R₂, R₃ and R₄ are hydrogen or C₁ -C₄ alkyl, especially hydrogen,

R₅ is hydrogen or is C₁ -C₈ alkyl which is unsubstituted or issubstituted by hydroxyl, sulfo or sulfato and, with the exception ofmethyl, is uninterrupted or is interrupted by oxygen, and in particularis hydrogen or C₁ -C₈ alkyl which is unsubstituted or substituted byhydroxyl and, with the exception of methyl, is uninterrupted orinterrupted by oxygen, and is preferably hydrogen,

B₁ is C₂ -C₁₂ alkylene which is uninterrupted or is interrupted byoxygen; or

is a methylene-cyclohexylene radical, cyclohexylene-methylene radical orcyclohexylene-methylene-cyclohexylene radical which is unsubstituted oris substituted in the cyclohexylene ring by C₁ -C₄ alkyl; or

is a methylene-phenylene-methylene radical which is unsubstituted or issubstituted in the phenylene ring by C₁ -C₄ alkyl, C₁ -C₄ alkoxy,halogen or sulfo,

B₂ is phenylene which is unsubstituted or is substituted by C₁ -C₄alkyl, C₁ -C₄ alkoxy, halogen or sulfo, and

Y is hydrogen or is C₁ -C₈ alkyl which is unsubstituted or issubstituted by hydroxyl, sulfo or sulfato and, with the exception ofmethyl, is uninterrupted or is interrupted by oxygen; or

is an anthraquinone radical of the formula (3); or

is sulfo-substituted naphthyl; or

is phenyl which can be substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy,halogen or sulfo or by a fibre-reactive radical of the formulae (2a),(2b), (2c) or (2d), where W is a group of the formula --CO--NH--, R ishydrogen and U₁ is sulfato or chlorine. Of particular interest in thiscontext are anthraquinone dyes in which B₁ is C₂ -C₆ alkylene and B₂ issulfo-substituted phenylene. R' is preferably hydrogen.

Preferred anthraquinone dyes of the formula (1) in which m is the number0 are those in which

Y is phenyl or naphthyl which is unsubstituted or is substituted by C₁-C₄ alkyl,

C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, halogen, carboxyl or sulfo, wherethe phenyl and naphthyl radicals contain at least one of thefibre-reactive groups of the formulae (2a) and (2b).

Particularly preferred anthraquinone dyes of the formula (I) in which mis the number 0 are those in which

R₁, R₂, R₃ and R₄ are hydrogen or C₁ -C₄ alkyl, especially hydrogen,

R₅ is hydrogen or is C₁ -C₈ alkyl which is unsubstituted or issubstituted by hydroxyl, sulfo or sulfato and, with the exception ofmethyl, is uninterrupted or is interrupted by oxygen, especiallyhydrogen or C₁ -C₈ alkyl which is unsubstituted or is substituted byhydroxyl and, with the exception of methyl, is uninterrupted or isinterrupted by oxygen, and is preferably hydrogen,

B₁ is C₂ -C₁₂ alkylene which is uninterrupted or is interrupted byoxygen; or

is a methylene-cyclohexylene radical, cyclohexylene-methylene radical orcyclohexylene-methylene-cyclohexylene radical which is unsubstituted oris substituted in the cyclohexylene ring by C₁ -C₄ alkyl; or

is a methylene-phenylene-methylene radical which is unsubstituted or issubstituted in the phenylene ring by C₁ -C₄ alkyl, C₁ -C₄ alkoxy,halogen or sulfo,

B₂ is phenylene which is unsubstituted or is substituted by C₁ -C₄alkyl, C₁ -C₄ alkoxy, halogen or sulfo, and

Y is phenyl which is unsubstituted or is substituted by C₁ -C₄ alkyl, C₁-C₄ alkoxy, halogen or sulfo, the phenyl radical containing at least oneof the fibre-reactive groups of the formulae (2a) and (2b). Ofparticular interest in this context are anthraquinone dyes in which B₁is C₂ -C₆ alkylene and B₂ is sulfo-substituted phenylene.

The present invention additionally provides a process for thepreparation of anthraquinone dyes of the formula (1), which comprisesreacting with one another compounds of the formulae ##STR7## cyanuricfluoride or cyanuric chloride and, if desired, a compound of the formula##STR8## with or without a subsequent conversion reaction, thedefinitions and preferences indicated above applying for R₁, R₂, R₃, R₄,R₅, B₁, B₂ and Y.

Since the individual process steps indicated above can be carried out ina variety of sequences, and in some cases even simultaneously, there isa variety of possible process variants. The reaction is generally cardedout stepwise in succession, with the sequence of the single reactionsbetween the individual reaction components depending advantageously onthe particular conditions.

For example, in order to prepare anthraquinone dyes of the formula (1)in which m is the number 0, a compound of the formula (5) is reactedwith cyanuric fluoride or cyanuric chloride and the resulting product isthen subjected to a condensation reaction with the compound of theformula (4).

A process variant for preparing anthraquinone dyes of the formula (1) inwhich m is the number 1 comprising reacting a compound of the formula(5) with cyanuric fluoride or cyanuric chloride, then reacting theresulting product with the compound of the formula (6), subjecting thatproduct to a condensation reaction with cyanuric fluoride or cyanuricchloride and then subjecting the resulting product to a condensationreaction with the compound of the formula (4).

A further process variant for preparing anthraquinone dyes of theformula (1) in which m is the number 1 comprises reacting a compound ofthe formula (6) with cyanuric fluoride or cyanuric chloride and thensubjecting the resulting product to a condensation reaction with thecompound of the formula (4). The product thus obtained is then reactedwith the product from the condensation of the compound of the formula(5) and cyanuric fluoride or cyanuric chloride.

In addition, as conversion reactions, elimination reactions can beappended to the synthesis. For example, anthraquinone dyes of theformula (1) which contain sulfatoethylsulfonyl radicals orα,β-dihalopropionylamino radicals can be treated with a base, forexample sodium hydroxide, in which case the sulfatoethylsulfonylradicals are converted to vinylsulfonyl radicals or theα,β-dihalopropionylamino radicals are converted to α-haloacryloylaminoradicals.

In principle, the anthraquinone dyes of the formula (1) can be preparedstarting from precursors or intermediates of dyes which containfibre-reactive radicals, or these fibre-reactive radicals are introducedinto intermediates suitable for this purpose which have the character ofdyes.

The compounds of the formulae (4), (5) and (6) are known or can beobtained in analogy to known compounds.

The individual condensation reactions take place, for example, inaccordance with processes which are known per se, generally in aqueoussolution at a temperature of, for example, from 0° to 50° C., inparticular from 0° to 10° C., and at a pH of, for example, from 4 to 10.

The dyes of the formula (1) according to the invention are either in theform of their free acid or, preferably, as the salts thereof. Examplesof suitable salts are the alkali metal, alkaline earth metal or ammoniumsalts or the salts of an organic amine. Examples are the sodium,lithium, potassium or ammonium salts or the salt of mono-, di- ortriethanolamine.

The dyes according to the invention are suitable for the dyeing andprinting of a very wide variety of materials, such ashydroxyl-containing or nitrogen-containing fibre materials. Examples aresilk, leather, wool, polyamide fibres and polyurethanes, and, inparticular, cellulose-containing fibre materials of all kinds. Examplesof such cellulose-containing fibre materials are the natural cellulosefibres such as cotton, linen and hemp, and also pulp and regeneratedcellulose. The dyes according to the invention are also suitable fordyeing or printing hydroxyl-containing fibres present in blend fabrics,for example blends of cotton with polyester fibres or polyamide fibres.The dyes according to the invention are particularly suitable for thedyeing or printing of cellulose-containing fibre-materials. In addition,they can be used to dye or print natural or synthetic polyamide fibrematerials, especially wool or synthetic polyamide fibre materials.

The dyes according to the invention can be applied to the fibrematerials and fixed on the fibre in various ways, in particular in theform of aqueous dye solutions and print pastes. They are suitable notonly for the exhaust method but also for dyeing by the padding method,in accordance with which the fabric is impregnated with aqueous dyesolutions which may or may not contain salt, and the dyes are fixedafter alkali treatment or in the presence of alkali, with or without theaction of heat. They are particularly suitable for the cold pad-batchprocess, according to which the dye together with the alkali is appliedto the padder and subsequently fixed by storage for several hours atroom temperature. After fixation, the dyeings or prints are rinsedthoroughly with cold and hot water, with or without the addition of adispersant which also promotes the diffusion of the unfixed portions.

The dyes according to the invention are distinguished by highreactivity, good fixation capacity and a very good buildup capacity.They can therefore be used by the exhaust dyeing method at low dyeingtemperatures and require only short steaming times in the pad-steammethod. The degrees of fixation are high, and the unfixed portions areeasy to wash off, the difference between the degree of exhaustion andthe degree of fixation being remarkably small, i.e. the loss on soapingbeing very low. The dyes according to the invention are alsoparticularly suitable for printing, especially on cotton, but also forprinting nitrogen-containing fibres, for example wool, silk or blendfabrics which include wool or silk.

The dyeings and prints produced using the dyes according to theinvention have a high colour strength and a high fibre-dye bondstability not only in the acid but also in the akaline range, and alsohave good light fastness and very good wet fastness properties, such aswash, water, salt water, cross-dyeing and perspiration fastnessproperties, and also good fastness to pleating, to hot pressing and torubbing.

The examples which follow are intended to illustrate the invention. Thetemperatures are indicated in degrees Celsius, parts are parts byweight, and the percentages are by weight, unless noted otherwise. Partsby weight relate to parts by volume as the kilogram to the liter.

EXAMPLE 1

19 parts of cyanuric chloride are stirred vigorously into 50 parts ofwater, with the addition of a wetting agent and 5 parts of disodiumhydrogen phosphate, at a temperature of 0° C. A neutral solution of 17parts of 2-aminobenzenesulfonic acid in 170 parts of water is addeddropwise. During this addition, the pH is kept constant at a value of4.5 by adding sodium hydroxide solution. After the end of reaction, asolution of 19 parts of 2,4-diaminobenzenesulfonic acid in 190 parts ofwater, which is rendered neutral with sodium hydroxide solution, isadded dropwise, with the pH being held constant at a value of 7 byaddition of sodium hydroxide solution. When starting material can nolonger be detected by thin-layer chromatography, the solution is addeddropwise to a suspension of 19 parts of cyanuric chloride in 50 parts ofwater which has been cooled to a temperature of 0° C. and is bufferedwith 5 parts of disodium hydrogen phosphate, the pH being held at avalue of 7 by addition of sodium hydroxide solution until condensationis complete.

To the solution thus obtained is added, dropwise, a further solution of38 parts of 1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonic acid,dissolved with 4 parts of lithium hydroxide monohydrate in 380 parts ofwater, at a rate such that the pH does not exceed a value of 10.Subsequently, the pH is maintained at a value of 9.5 until the end ofthe reaction. Following neutralization, the sodium chloride formed isremoved by dialysis and the dye solution is concentrated by evaporationin vacuo. A dye is obtained which in the form of the free acidcorresponds to the compound of the formula ##STR9##

The dye of the formula (101) dyes cotton and wool in blue shades.

EXAMPLE 2

19 parts of cyanuric chloride are stirred vigorously into 50 parts ofwater, with the addition of a wetting agent and 5 parts of disodiumhydrogen phosphate, at a temperature of 0° C. A neutral solution of 19parts of 2,4-diaminobenzenesulfonic acid in 190 parts of water is addeddropwise. During this addition the pH is kept constant at a value of 4.5by addition of sodium hydroxide solution. The resulting solution isadded dropwise to a solution of 38 parts of1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonic acid, dissolved with 4parts of lithium hydroxide monohydrate in 380 parts of water, at a ratesuch that the pH does not exceed a value of 10. The pH is subsequentlykept at a value of 9.5 until the end of the reaction (solution 1).

19 parts of cyanuric chloride are stirred vigorously into 50 parts ofwater, with the addition of a wetting agent and 5 parts of disodiumhydrogen phosphate, at a temperature of 0° C. A neutral solution of 17parts of 2-aminobenzenesulfonic acid in 170 parts of water is added.During this addition, the pH is held constant at a value of 4.5 byaddition of sodium hydroxide solution. The solution 1 obtainable asindicated above is added dropwise to this solution at a rate such thatthe pH does not exceed a value of 7. The pH is then held at a value of 7until the end of the reaction. The sodium chloride formed is removed bydialysis and the dye solution is concentrated by evaporation in vacuo. Adye is obtained which in the form of the free acid corresponds to thecompound of the formula ##STR10##

The dye of the formula (102) dyes cotton and wool in blue shades.

EXAMPLES 3 TO 305

Following the procedure of Example 1 or of Example 2 but using

instead of 17 parts of 2-aminobenzenesulfonic acid, an equimolarquantity of an amine of the formula H--V₁, and

instead of 38 parts of 1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonicacid, an equimolar quantity of an anthraquinone compound of the formula##STR11## gives the dyes indicated in Table 1 below of the generalformula ##STR12## respectively, where B₁ and V₁ are in each case definedas indicated in Table 1 below. The dyes indicated in Table 1 dye cottonand wool in blue shades.

                                      TABLE 1                                     __________________________________________________________________________    Ex.                                                                              V.sub.1                      B.sub.1                                       __________________________________________________________________________     3                                                                                ##STR13##                   (CH.sub.2).sub.6                               4                                                                                ##STR14##                   (CH.sub.2).sub.6                               5                                                                                ##STR15##                   (CH.sub.2).sub.6                               6                                                                                ##STR16##                   (CH.sub.2).sub.6                               7                                                                                ##STR17##                   (CH.sub.2).sub.6                               8                                                                                ##STR18##                   (CH.sub.2).sub.6                               9                                                                                ##STR19##                   (CH.sub.2).sub.6                              10                                                                                ##STR20##                   (CH.sub.2).sub.6                              11                                                                                ##STR21##                   (CH.sub.2).sub.6                              12                                                                                ##STR22##                   (CH.sub.2).sub.6                              13                                                                                ##STR23##                   (CH.sub.2).sub.6                              14                                                                                ##STR24##                   (CH.sub.2).sub.6                              15                                                                                ##STR25##                   (CH.sub.2).sub.6                              16                                                                                ##STR26##                   (CH.sub.2).sub.6                              17                                                                                ##STR27##                   (CH.sub.2).sub.6                              18                                                                                ##STR28##                   (CH.sub.2).sub.6                              19                                                                                ##STR29##                   (CH.sub.2).sub.6                              20                                                                                ##STR30##                   (CH.sub.2).sub.6                              21                                                                                ##STR31##                   (CH.sub.2).sub.6                              22                                                                                ##STR32##                   (CH.sub.2).sub.6                              23                                                                                ##STR33##                   (CH.sub.2).sub.6                              24                                                                                ##STR34##                   (CH.sub.2).sub.6                              25                                                                                ##STR35##                   (CH.sub.2).sub.6                              26                                                                                ##STR36##                   (CH.sub.2).sub.6                              27                                                                                ##STR37##                   (CH.sub.2).sub.6                              28                                                                                ##STR38##                   (CH.sub.2).sub.6                              29                                                                                ##STR39##                   (CH.sub.2).sub.6                              30 NHCH.sub.2 CH.sub.2SO.sub.3 H                                                                              (CH.sub.2).sub.6                              31                                                                                ##STR40##                   (CH.sub.2).sub.6                              32 NH.sub.2                     (CH.sub.2).sub.6                              33 NHCH.sub.2 CH.sub.2OH        (CH.sub.2).sub.6                              34                                                                                ##STR41##                   (CH.sub.2).sub.6                              35 NHCH.sub.2 CH.sub.2OCH.sub.3 (CH.sub.2).sub.6                              36 NHCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OH                                                                    (CH.sub.2).sub.6                              37                                                                                ##STR42##                   (CH.sub.2).sub.6                              38                                                                                ##STR43##                   (CH.sub.2).sub.6                              39                                                                                ##STR44##                   (CH.sub.2).sub.6                              40                                                                                ##STR45##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      41                                                                                ##STR46##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      42                                                                                ##STR47##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      43                                                                                ##STR48##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      44                                                                                ##STR49##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      45                                                                                ##STR50##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      46                                                                                ##STR51##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      47                                                                                ##STR52##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      48                                                                                ##STR53##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      49                                                                                ##STR54##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      50                                                                                ##STR55##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      51                                                                                ##STR56##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      52                                                                                ##STR57##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      53                                                                                ##STR58##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      54                                                                                ##STR59##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      55                                                                                ##STR60##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      56                                                                                ##STR61##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      57                                                                                ##STR62##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      58                                                                                ##STR63##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      59                                                                                ##STR64##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      60                                                                                ##STR65##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      61                                                                                ##STR66##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      62                                                                                ##STR67##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      63                                                                                ##STR68##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      64                                                                                ##STR69##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      65                                                                                ##STR70##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      66                                                                                ##STR71##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      67                                                                                ##STR72##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      68 NHCH.sub.2 CH.sub.2SO.sub.3 H                                                                              (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      69                                                                                ##STR73##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      70 NH.sub.2                     (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      71 NNHCH.sub.2 CH.sub.2OH       (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      72                                                                                ##STR74##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      73 NHCH.sub.2 CH.sub.2OCH.sub.3 (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      74 NHCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OH                                                                    (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      75                                                                                ##STR75##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      76                                                                                ##STR76##                   (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.                                    2).sub.2                                      77                                                                                ##STR77##                                                                 78                                                                                ##STR78##                                                                                                  ##STR79##                                    79                                                                                ##STR80##                                                                                                  ##STR81##                                    80                                                                                ##STR82##                                                                                                  ##STR83##                                    81                                                                                ##STR84##                                                                                                  ##STR85##                                    82                                                                                ##STR86##                                                                                                  ##STR87##                                    83                                                                                ##STR88##                                                                                                  ##STR89##                                    84                                                                                ##STR90##                                                                                                  ##STR91##                                    85                                                                                ##STR92##                                                                                                  ##STR93##                                    86                                                                                ##STR94##                                                                                                  ##STR95##                                    87                                                                                ##STR96##                                                                                                  ##STR97##                                    88                                                                                ##STR98##                                                                                                  ##STR99##                                    89                                                                                ##STR100##                                                                                                 ##STR101##                                   90                                                                                ##STR102##                                                                                                 ##STR103##                                   91                                                                                ##STR104##                                                                                                 ##STR105##                                   92                                                                                ##STR106##                                                                                                 ##STR107##                                   93                                                                                ##STR108##                                                                                                 ##STR109##                                   94                                                                                ##STR110##                                                                                                 ##STR111##                                   95                                                                                ##STR112##                                                                                                 ##STR113##                                   96                                                                                ##STR114##                                                                                                 ##STR115##                                   97                                                                                ##STR116##                                                                                                 ##STR117##                                   98                                                                                ##STR118##                                                                                                 ##STR119##                                   99                                                                                ##STR120##                                                                                                 ##STR121##                                   100                                                                               ##STR122##                                                                                                 ##STR123##                                   101                                                                               ##STR124##                                                                                                 ##STR125##                                   102                                                                               ##STR126##                                                                                                 ##STR127##                                   103                                                                               ##STR128##                                                                                                 ##STR129##                                   104                                                                               ##STR130##                                                                                                 ##STR131##                                   105                                                                               ##STR132##                                                                                                 ##STR133##                                   106                                                                              NHCH.sub.2 CH.sub.2SO.sub.3 H                                                                               ##STR134##                                   107                                                                               ##STR135##                                                                                                 ##STR136##                                   108                                                                              NH.sub.2                                                                                                    ##STR137##                                   109                                                                              NHCH.sub.2 CH.sub.2OH                                                                                       ##STR138##                                   110                                                                               ##STR139##                                                                                                 ##STR140##                                   111                                                                              NHCH.sub.2 CH.sub.2OCH.sub.3                                                                                ##STR141##                                   112                                                                              NNHCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OH                                                                    ##STR142##                                   113                                                                               ##STR143##                                                                                                 ##STR144##                                   114                                                                               ##STR145##                                                                                                 ##STR146##                                   115                                                                               ##STR147##                                                                                                 ##STR148##                                   116                                                                               ##STR149##                                                                                                 ##STR150##                                   117                                                                               ##STR151##                                                                                                 ##STR152##                                   118                                                                               ##STR153##                                                                                                 ##STR154##                                   119                                                                               ##STR155##                                                                                                 ##STR156##                                   120                                                                               ##STR157##                                                                                                 ##STR158##                                   121                                                                               ##STR159##                                                                                                 ##STR160##                                   122                                                                               ##STR161##                                                                                                 ##STR162##                                   123                                                                               ##STR163##                                                                                                 ##STR164##                                   124                                                                               ##STR165##                                                                                                 ##STR166##                                   125                                                                               ##STR167##                                                                                                 ##STR168##                                   126                                                                               ##STR169##                                                                                                 ##STR170##                                   127                                                                               ##STR171##                                                                                                 ##STR172##                                   128                                                                               ##STR173##                                                                                                 ##STR174##                                   129                                                                               ##STR175##                                                                                                 ##STR176##                                   130                                                                               ##STR177##                                                                                                 ##STR178##                                   131                                                                               ##STR179##                                                                                                 ##STR180##                                   132                                                                               ##STR181##                                                                                                 ##STR182##                                   133                                                                               ##STR183##                                                                                                 ##STR184##                                   134                                                                               ##STR185##                                                                                                 ##STR186##                                   135                                                                               ##STR187##                                                                                                 ##STR188##                                   136                                                                               ##STR189##                                                                                                 ##STR190##                                   137                                                                               ##STR191##                                                                                                 ##STR192##                                   138                                                                               ##STR193##                                                                                                 ##STR194##                                   139                                                                               ##STR195##                                                                                                 ##STR196##                                   140                                                                               ##STR197##                                                                                                 ##STR198##                                   141                                                                               ##STR199##                                                                                                 ##STR200##                                   142                                                                               ##STR201##                                                                                                 ##STR202##                                   143                                                                               ##STR203##                                                                                                 ##STR204##                                   144                                                                              NHCH.sub.2 CH.sub.2SO.sub.3 H                                                                               ##STR205##                                   145                                                                               ##STR206##                                                                                                 ##STR207##                                   146                                                                              NH.sub.2                                                                                                    ##STR208##                                   147                                                                              NHCH.sub.2 CH.sub.2OH                                                                                       ##STR209##                                   148                                                                               ##STR210##                                                                                                 ##STR211##                                   149                                                                              NHCH.sub.2 CH.sub.2OCH.sub.3                                                                                ##STR212##                                   150                                                                              NHCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OH                                                                     ##STR213##                                   151                                                                               ##STR214##                                                                                                 ##STR215##                                   152                                                                               ##STR216##                                                                                                 ##STR217##                                   153                                                                               ##STR218##                                                                                                 ##STR219##                                   154                                                                               ##STR220##                                                                                                 ##STR221##                                   155                                                                               ##STR222##                                                                                                 ##STR223##                                   156                                                                               ##STR224##                                                                                                 ##STR225##                                   157                                                                               ##STR226##                                                                                                 ##STR227##                                   158                                                                               ##STR228##                                                                                                 ##STR229##                                   159                                                                               ##STR230##                                                                                                 ##STR231##                                   160                                                                               ##STR232##                                                                                                 ##STR233##                                   161                                                                               ##STR234##                                                                                                 ##STR235##                                   162                                                                               ##STR236##                                                                                                 ##STR237##                                   163                                                                               ##STR238##                                                                                                 ##STR239##                                   164                                                                               ##STR240##                                                                                                 ##STR241##                                   165                                                                               ##STR242##                                                                                                 ##STR243##                                   166                                                                               ##STR244##                                                                                                 ##STR245##                                   167                                                                               ##STR246##                                                                                                 ##STR247##                                   168                                                                               ##STR248##                                                                                                 ##STR249##                                   169                                                                               ##STR250##                                                                                                 ##STR251##                                   170                                                                               ##STR252##                                                                                                 ##STR253##                                   171                                                                               ##STR254##                                                                                                 ##STR255##                                   172                                                                               ##STR256##                                                                                                 ##STR257##                                   173                                                                               ##STR258##                                                                                                 ##STR259##                                   174                                                                               ##STR260##                                                                                                 ##STR261##                                   175                                                                               ##STR262##                                                                                                 ##STR263##                                   176                                                                               ##STR264##                                                                                                 ##STR265##                                   177                                                                               ##STR266##                                                                                                 ##STR267##                                   178                                                                               ##STR268##                                                                                                 ##STR269##                                   179                                                                               ##STR270##                                                                                                 ##STR271##                                   180                                                                               ##STR272##                                                                                                 ##STR273##                                   181                                                                               ##STR274##                                                                                                 ##STR275##                                   182                                                                              NHCH.sub.2 CH.sub.2SO.sub.3 H                                                                               ##STR276##                                   183                                                                               ##STR277##                                                                                                 ##STR278##                                   184                                                                              NH.sub.2                                                                                                    ##STR279##                                   185                                                                              NHCH.sub.2 CH.sub.2OH                                                                                       ##STR280##                                   186                                                                               ##STR281##                                                                                                 ##STR282##                                   187                                                                              NHCH.sub.2 CH.sub.2OCH.sub.3                                                                                ##STR283##                                   188                                                                              NHCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OH                                                                     ##STR284##                                   189                                                                               ##STR285##                                                                                                 ##STR286##                                   190                                                                               ##STR287##                                                                                                 ##STR288##                                   191                                                                               ##STR289##                                                                                                 ##STR290##                                   192                                                                               ##STR291##                                                                                                 ##STR292##                                   193                                                                               ##STR293##                                                                                                 ##STR294##                                   194                                                                               ##STR295##                                                                                                 ##STR296##                                   195                                                                               ##STR297##                                                                                                 ##STR298##                                   196                                                                               ##STR299##                                                                                                 ##STR300##                                   197                                                                               ##STR301##                                                                                                 ##STR302##                                   198                                                                               ##STR303##                                                                                                 ##STR304##                                   199                                                                               ##STR305##                                                                                                 ##STR306##                                   200                                                                               ##STR307##                                                                                                 ##STR308##                                   201                                                                               ##STR309##                                                                                                 ##STR310##                                   202                                                                               ##STR311##                                                                                                 ##STR312##                                   203                                                                               ##STR313##                                                                                                 ##STR314##                                   204                                                                               ##STR315##                                                                                                 ##STR316##                                   205                                                                               ##STR317##                                                                                                 ##STR318##                                   206                                                                               ##STR319##                                                                                                 ##STR320##                                   207                                                                               ##STR321##                                                                                                 ##STR322##                                   208                                                                               ##STR323##                                                                                                 ##STR324##                                   209                                                                               ##STR325##                                                                                                 ##STR326##                                   210                                                                               ##STR327##                                                                                                 ##STR328##                                   211                                                                               ##STR329##                                                                                                 ##STR330##                                   212                                                                               ##STR331##                                                                                                 ##STR332##                                   213                                                                               ##STR333##                                                                                                 ##STR334##                                   214                                                                               ##STR335##                                                                                                 ##STR336##                                   215                                                                               ##STR337##                                                                                                 ##STR338##                                   216                                                                               ##STR339##                                                                                                 ##STR340##                                   217                                                                               ##STR341##                                                                                                 ##STR342##                                   218                                                                               ##STR343##                                                                                                 ##STR344##                                   219                                                                               ##STR345##                                                                                                 ##STR346##                                   220                                                                              NHCH.sub.2 CH.sub.2SO.sub.3 H                                                                               ##STR347##                                   221                                                                               ##STR348##                                                                                                 ##STR349##                                   222                                                                              NNH.sub.2                                                                                                   ##STR350##                                   223                                                                              NHCH.sub.2 CH.sub.2OH                                                                                       ##STR351##                                   224                                                                               ##STR352##                                                                                                 ##STR353##                                   225                                                                              NHCH.sub.2 CH.sub.2OCH.sub.3                                                                                ##STR354##                                   226                                                                              NHCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OH                                                                     ##STR355##                                   227                                                                               ##STR356##                                                                                                 ##STR357##                                   228                                                                               ##STR358##                                                                                                 ##STR359##                                   229                                                                               ##STR360##                                                                                                 ##STR361##                                   230                                                                               ##STR362##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      231                                                                               ##STR363##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      232                                                                               ##STR364##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      233                                                                               ##STR365##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      234                                                                               ##STR366##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      235                                                                               ##STR367##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      236                                                                               ##STR368##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      237                                                                               ##STR369##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      238                                                                               ##STR370##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      239                                                                               ##STR371##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      240                                                                               ##STR372##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      241                                                                               ##STR373##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      242                                                                               ##STR374##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      243                                                                               ##STR375##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      244                                                                               ##STR376##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      245                                                                               ##STR377##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      246                                                                               ##STR378##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      247                                                                               ##STR379##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      248                                                                               ##STR380##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      249                                                                               ##STR381##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      250                                                                               ##STR382##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      251                                                                               ##STR383##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      252                                                                               ##STR384##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      253                                                                               ##STR385##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      254                                                                               ##STR386##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      255                                                                               ##STR387##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      256                                                                               ##STR388##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      257                                                                               ##STR389##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      258                                                                              NHCH.sub.2 CH.sub.2SO.sub.3 H                                                                              (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      259                                                                               ##STR390##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      260                                                                              NH.sub.2                     (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      261                                                                              NHCH.sub.2 CH.sub.2OH        (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      262                                                                               ##STR391##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      263                                                                              NHCH.sub.2 CH.sub.2OCH.sub.3 (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      264                                                                              NNHCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OH                                                                   (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      265                                                                               ##STR392##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      266                                                                               ##STR393##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      267                                                                               ##STR394##                  (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.                                    2).sub.3                                      268                                                                               ##STR395##                  (CH.sub.2).sub.3                              269                                                                               ##STR396##                  (CH.sub.2).sub.3                              270                                                                               ##STR397##                  (CH.sub.2).sub.3                              271                                                                               ##STR398##                  (CH.sub.2).sub.3                              272                                                                               ##STR399##                  (CH.sub.2).sub.3                              273                                                                               ##STR400##                  (CH.sub.2).sub.3                              274                                                                               ##STR401##                  (CH.sub.2).sub.3                              275                                                                               ##STR402##                  (CH.sub.2).sub.3                              276                                                                               ##STR403##                  (CH.sub.2).sub.3                              277                                                                               ##STR404##                  (CH.sub.2).sub.3                              278                                                                               ##STR405##                  (CH.sub.2).sub.3                              279                                                                               ##STR406##                  (CH.sub.2).sub.3                              280                                                                               ##STR407##                  (CH.sub.2).sub.3                              281                                                                               ##STR408##                  (CH.sub.2).sub.3                              282                                                                               ##STR409##                  (CH.sub.2).sub.3                              283                                                                               ##STR410##                  (CH.sub.2).sub.3                              284                                                                               ##STR411##                  (CH.sub.2).sub.3                              285                                                                               ##STR412##                  (CH.sub.2).sub.3                              286                                                                               ##STR413##                  (CH.sub.2).sub.3                              287                                                                               ##STR414##                  (CH.sub.2).sub.3                              288                                                                               ##STR415##                  (CH.sub.2).sub.3                              289                                                                               ##STR416##                  (CH.sub.2).sub.3                              290                                                                               ##STR417##                  (CH.sub.2).sub.3                              291                                                                               ##STR418##                  (CH.sub.2).sub.3                              292                                                                               ##STR419##                  (CH.sub.2).sub.3                              293                                                                               ##STR420##                  (CH.sub.2).sub.3                              294                                                                               ##STR421##                  (CH.sub.2).sub.3                              295                                                                              NHCH.sub.2 CH.sub.2SO.sub.3 H                                                                              (CH.sub.2).sub.3                              296                                                                               ##STR422##                  (CH.sub.2).sub.3                              297                                                                              NH.sub.2                     (CH.sub.2).sub.3                              298                                                                              NNHCH.sub.2 CH.sub.2OH       (CH.sub.2).sub.3                              299                                                                               ##STR423##                  (CH.sub.2).sub.3                              300                                                                              NHCH.sub.2 CH.sub.2OCH.sub.3 (CH.sub.2).sub.3                              301                                                                              NHCH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2OH                                                                    (CH.sub.2).sub.3                              302                                                                               ##STR424##                  (CH.sub.2).sub.3                              303                                                                               ##STR425##                  (CH.sub.2).sub.3                              304                                                                               ##STR426##                  (CH.sub.2).sub.3                              305                                                                               ##STR427##                  (CH.sub.2).sub.6                              __________________________________________________________________________

Following the procedure of Example 1 but using

instead of 38 parts of 1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonicacid, an equimolar quantity of an anthraquinone compound of the formula##STR428## gives analogous dyes which dye cotton and wool in blueshades.

Following the procedure indicated in one of Examples 1 to 305 but using,instead of 19 parts of 2,4-diaminobenzenesulfonic acid, an equimolarquantity of

2,5-diaminobenzenesulfonic acid,

2,4-diaminobenzene-1,5-disulfonic acid or

2,5-diaminobenzene-1,4-disulfonic acid gives analogous dyes which dyecotton and wool in blue shades.

EXAMPLE 306

By a procedure similar to that indicated in Example 2, the dye of theformula ##STR429## can be obtained. The dye of the formula (105) dyescotton and wool in blue shades.

EXAMPLE 307

13 parts of cyanuric fluoride are added dropwise at a temperature of 0°C. to a solution of 17 parts of 2-aminobenzenesulfonic acid in 250 partsof water, which has been rendered neutral with sodium hydroxide solutionand is buffered with 5 parts of disodium hydrogen phosphate. During thisdropwise addition, the pH is held constant at a value of 7 by additionof sodium hydroxide solution. After the end of the reaction, a solutionof 19 parts of 2,4-diaminobenzenesulfonic acid in 150 parts of water,rendered neutral with sodium hydroxide solution, is added dropwise, thepH being held constant at a value of 7 by addition of sodium hydroxidesolution. When starting material can no longer be detected by thin-layerchromatography, 13 parts of cyanuric fluoride are added dropwise, the pHbeing held at a value of 7 by addition of sodium hydroxide solution.

To the solution thus obtained is added dropwise a further solution of 38parts of 1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonic acid,dissolved with 4 parts of lithium hydroxide monohydrate in 380 parts ofwater, at a rate such that the pH does not exceed a value of 10. The pHis subsequently held at a value of 9.5 until the end of the reaction.Following neutralization, the sodium chloride formed is removed bydialysis and the dye solution is concentrated by evaporation in vacuo. Adye is obtained which in the form of the free acid corresponds to thecompound of the formula ##STR430##

The dye of the formula (106) dyes cotton and wool in blue shades.

EXAMPLE 308

13 parts of cyanuric fluoride are added dropwise at a temperature of 0°C. to a solution of 19 parts of 2,4-diaminobenzenesulfonic acid in 150parts of water, which has been rendered neutral with sodium hydroxidesolution and is buffered with 5 parts of disodium hydrogen phosphate.During this dropwise addition, the pH is held constant at a value of 5by addition of sodium hydroxide solution. After the end of the reaction,the resulting solution is added dropwise to a solution of 38 parts of1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonic acid, dissolved with 4parts of lithium hydroxide monohydrate in 380 parts of water, at a ratesuch that the pH does not exceed a value of 9. The pH is subsequentlyheld at a value of 8.5 until the end of the reaction (solution 1).

13 parts of cyanuric fluoride are added dropwise at a temperature of 0°C. to a solution of 17 parts of 2-aminobenzenesulfonic acid in 250 partsof water, which has been rendered neutral with sodium hydroxide solutionand is buffered with 5 parts of disodium hydrogen phosphate. During thisdropwise addition, the pH is held constant at a value of 7 by additionof sodium hydroxide solution. The solution 1 obtainable as indicatedabove is subsequently added dropwise at a rate such that the pH does notexceed a value of 7. The pH is then held at the value of 7 by addingsodium hydroxide solution. After the end of the reaction, the sodiumchloride formed is removed by dialysis and the dye solution isconcentrated by evaporation in vacuo. A dye is obtained which in theform a free acid corresponds to the compound of the formula ##STR431##

The dye of the formula (107) dyes cotton and wool in blue shades.

Following the procedure of Example 307 or of Example 308 but using,instead of 17 parts of 2-aminobenzenesulfonic acid, an equimolarquantity of an amine of the formula H--V₁, and,

instead of 38 parts of 1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonic acid, an equimolarquantity of an anthraquinone compound of the formula (103), where B₁ andV₁ are in each case as defined in Examples 3 to 305 of Table 1, givesdyes of the general formula ##STR432## respectively, in which B₁ and V₁are in each case as defined in Examples 3 to 305 of Table 1, and whichdye cotton and wool in blue shades.

Analogous dyes are obtained using, instead of 19 parts of2,4-diaminobenzenesulfonic acid, an equimolar quantity of

2,5-diaminobenzenesulfonic acid,

2,4-diaminobenzene-1,5-disulfonic acid or

2,5-diaminobenzene-1,4-disulfonic acid.

EXAMPLE 309

Following the procedure indicated in Example 308, the dye of the formula##STR433## can be obtained. The dye of the formula (109) dyes cotton andwool in blue shades.

EXAMPLE 310

19 parts of cyanuric chloride are stirred vigorously into 50 parts ofwater, with the addition of a wetting agent and 5 parts of disodiumhydrogen phosphate, at a temperature of 0° C. A neutral solution of 32parts of a compound of the formula ##STR434## in 320 parts of water isadded. During this addition, the pH is held constant at a value of 4.5by addition of sodium hydroxide solution. After the end of the reaction,a solution of 38 parts of1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonic acid, dissolved with 4parts of lithium hydroxide monohydrate in 380 parts of water, is addeddropwise at a rate such that the pH does not exceed a value of 10. ThepH is subsequently held at a value of 9.5 until the end of the reaction.The dye is precipitated by addition of sodium chloride, filtered off,washed with aqueous sodium chloride solution and dried. A dye isobtained which in the form of the free acid corresponds to the compoundof the formula ##STR435##

The dye of the formula (111) dyes cotton and wool in blue shades.

EXAMPLES 311 TO 344

Following the procedure of Example 310 but using, instead of 32 parts ofa compound of the formula (110), an equimolar quantity of an amine ofthe formula H--V₁, and,

instead of 38 parts of 1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonicacid, an equimolar quantity of an anthraquinone compound of the formula##STR436## gives the dyes indicated in Table 2 below of the generalformula ##STR437## in which B₁ and V₁ are in each case as defined inTable 2 below.

The dyes indicated in Table 2 dye cotton and wool in blue shades.

                                      TABLE 2                                     __________________________________________________________________________    Ex.                                                                              V.sub.1               B.sub.1                                              __________________________________________________________________________    311                                                                               ##STR438##           (CH.sub.2).sub.3                                     312                                                                               ##STR439##           (CH.sub.2).sub.3                                     313                                                                               ##STR440##           (CH.sub.2).sub.3                                     314                                                                               ##STR441##           (CH.sub.2).sub.6                                     315                                                                               ##STR442##           (CH.sub.2).sub.6                                     316                                                                               ##STR443##           (CH.sub.2).sub.6                                     317                                                                               ##STR444##           (CH.sub.2).sub.6                                     318                                                                               ##STR445##           (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.2).sub.                             2                                                    319                                                                               ##STR446##           (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.2).sub.                             2                                                    320                                                                               ##STR447##           (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.2).sub.                             2                                                    321                                                                               ##STR448##           (CH.sub.2).sub.2O(CH.sub.2).sub.2O(CH.sub.2).sub.                             2                                                    322                                                                               ##STR449##                                                                                          ##STR450##                                          323                                                                               ##STR451##                                                                                          ##STR452##                                          324                                                                               ##STR453##                                                                                          ##STR454##                                          325                                                                               ##STR455##                                                                                          ##STR456##                                          326                                                                               ##STR457##           CH.sub.2C(CH.sub.3).sub.2CH.sub.2                    327                                                                               ##STR458##           CH.sub.2C(CH.sub.3).sub.2CH.sub.2                    328                                                                               ##STR459##           CH.sub.2C(CH.sub.3).sub.2CH.sub.2                    329                                                                               ##STR460##           CH.sub.2C(CH.sub.3).sub.2CH.sub.2                    330                                                                               ##STR461##                                                                                          ##STR462##                                          331                                                                               ##STR463##                                                                                          ##STR464##                                          332                                                                               ##STR465##                                                                                          ##STR466##                                          333                                                                               ##STR467##                                                                                          ##STR468##                                          334                                                                               ##STR469##                                                                                          ##STR470##                                          335                                                                               ##STR471##                                                                                          ##STR472##                                          336                                                                               ##STR473##                                                                                          ##STR474##                                          337                                                                               ##STR475##                                                                                          ##STR476##                                          338                                                                               ##STR477##           (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.2).sub.                             3                                                    339                                                                               ##STR478##           (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.2).sub.                             3                                                    340                                                                               ##STR479##           (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.2).sub.                             3                                                    341                                                                               ##STR480##           (CH.sub.2).sub.3O(CH.sub.2).sub.4O(CH.sub.2).sub.                             3                                                    342                                                                               ##STR481##           CH.sub.2CH.sub.2CH(C.sub.2 H.sub.5)                  343                                                                               ##STR482##           CH.sub.2CH(OH)CH.sub.2                               344                                                                               ##STR483##           CH.sub.2CH(OH)CH.sub.2                               __________________________________________________________________________

Following the procedure of Example 310 but using,

instead of 38 parts of 1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonicacid, an eqimolar quantity of an anthraquinone compound of the formula##STR484## gives analogous dyes which dye cotton and wool in blueshades.

EXAMPLE 345

13 parts of cyanuric fluoride are added dropwise at a temperature of 0°C. to a solution of 32 parts of a compound of the formula ##STR485## in320 parts of water, which has been rendered neutral with sodiumhydroxide solution and is buffered with 5 parts of disodium hydrogenphosphate. During this dropwise addition, the pH is held constant at avalue of 7 by addition of sodium hydroxide solution. After the end ofthe reaction, a solution of 38 parts of1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonic acid, dissolved with 4parts of lithium hydroxide monohydrate in 380 parts of water, is addeddropwise at a rate such that the pH does not exceed a value of 10. ThepH is subsequently held at a value of 9.5 until the end of the reaction.The dye is precipitated by addition of sodium chloride, filtered off,washed with aqueous sodium chloride solution and dried. A dye isobtained which in the form of the free acid corresponds to the compoundof the formula ##STR486##

The dye of the formula (113) dyes cotton and wool in blue shades.

Following the procedure of Example 345 but using, instead of 32 parts ofa compound of the formula (110), an equimolar quantity of an amine ofthe formula H--V₁, and,

instead of 38 parts of 1-amino-4-(3-aminopropyl)anthraquinone-2-sulfonicacid, an equimolar quantity of an anthraquinone compound of the formula(103) in which B₁ and V₁ are in each case as defined in Examples 311 to344 of Table 2, gives dyes of the general formula ##STR487## in which B₁and V₁ are in each case as defined in Examples 311 to 344 of Table 2 andwhich dye cotton and wool in blue shades.

In the examples in which a product containing a β-sulfatoethylsulfonylgroup or α,β-dibromopropionylamino group is reacted with ananthraquinone compound, this reaction is carried out in a relativelydilute medium at a pH of about 8.5.

Dyeing method

2 parts of the reactive dye obtained according to Example 1 aredissolved in 400 parts of water, 1500 parts of a solution containing 53g of sodium chloride per liter are added. This dyebath is entered at 40°C. with 100 parts of cotton fabric. After 45 minutes 100 parts of asolution containing 16 g of sodium hydroxide and 20 g of calcined sodiumcarbonate per liter are added. The temperature of the dyebath is held at40° C. for a further 45 minutes. Then the dyed fabric is rinsed, soapedoff at the boil for a quarter of an hour with a nonionic detergent,rinsed once more and dried.

Printing method

3 parts of the reactive dye obtained according to Example 1 aresprinkled with rapid stirring into 100 parts of a stock thickeningcontaining 50 parts of 5% sodium alginate thickening, 27.8 parts ofwater, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and1.2 parts of sodium hydrogen carbonate. The resulting print paste isused to print a cotton fabric, which is then dried and steamed at 102°C. in saturated steam for 2 minutes. The printed fabric is then rinsed,soaped off at the boil if desired and rinsed once more, and subsequentlydried.

What is claimed is:
 1. An anthraquinone dye of the formula ##STR488## inwhich R₁, R₂, R₃, R₄ and R₅ independently of one another are hydrogen orare substituted or unsubstituted C₁ -C₁₄ alkyl,X₁ and X₂ independentlyof one another are chlorine or fluorine, B₁ is a bridge member offormula --(CH₂)₆ --, --(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --, --(CH₂)₃--O--(CH₂)₄ --O--(CH₂)₃ --, --CH₂ --CH₂ --CH(C₂ H₅)--, --(CH₂)₃--CH(CH₃)--CH₂ -- or --CH₂ --C(CH₃)₂ --CH₂ --, B₂ is an aromatic bridgemember, and Y is an anthraquinone radical of the formula ##STR489## inwhich B₁ ' is as defined above for B₁.
 2. An anthraquinone dye accordingto claim 1, in whichR₁, R₂, R₃ and R₄ are hydrogen or C₁ -C₄ alkyl andR₅ is hydrogen or is C₁ -C₈ alkyl which is unsubstituted or issubstituted by hydroxyl, sulfo or sulfato and, with the exception ofmethyl, is uninterrupted or is interrupted by oxygen.
 3. Ananthraquinone dye according to claim 1, in whichB₁ and B₁ ' are --CH₂--C(CH₃)₂ --CH₂ --.
 4. An anthraquinone dye according to claim 1, inwhichB₂ is phenylene or naphthalene which is unsubstituted or issubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino,halogen, carboxyl or sulfo.
 5. An anthraquinone dye according to claim1, in whichB₂ is phenylene which is unsubstituted or is substituted byC₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen or sulfo.
 6. An anthraquinone dyeaccording to claim 1, in whichB₁ and B₁ ' are --CH₂ --C(CH₃)₂ --CH₂ --and B₂ is sulfo-substituted phenylene.
 7. A process for the preparationof an anthraquinone dye according to claim 1, which comprises reactingwith one another compounds of the formulae ##STR490## cyanuric fluorideor cyanuric chloride and, a compound of the formula ##STR491## with orwithout a subsequent conversion reaction, R₁, R₂, R₃, R₄, R₅, B₁, B₂ andY being as defined in claim
 1. 8. A process for the dyeing or printingof a hydroxyl-containing or nitrogen-containing fibre material, whichcomprises applying to said fibre material a tinctorially effectiveamount of an anthraquinone dye according to claim
 1. 9. The processaccording to claim 8 for the dyeing or printing of cellulose-containingfibre material or natural or synthetic polyamide fibre material.